Phenolic and naphtholic couplers containing sulphonamide groups



obtained'do not always have Patented Aug. 22, 1944 I .PI-IENOLIC AND NAPH'IHOLIC (IOUPLERS CONTAINING SULPIIONAMIDE GROUPS Karl Schinzel, Zurich, Switzerland, assiznor to Eastman Kodak Company, Rochester; N. Y., a corporation oi. New Jersey No Drawing. Application March 24, 1939, Serial No. 263,945. In Austria July 7, 1936 12 Claims. (Cl. 956) This invention relates to photographic color forming compoundsand more particularly to phenolic or naphtholic coupler compounds con taining a sulphonamide group.

This application is a continuation in part of my Patent 1942.

, The formation of colored photographic images by the use of a primary aromatic amino developing agent, which couples with a color forming compound ondevelopment, has been the subject of prior patents. Fischer British Patent 15,055/19l2 discloses phenols and naphthols as coupler compounds which are used with p-phenylenediamine couplers. These coupler compounds react with the developing. agent during photographic development to form colored photographic images. 'The dyes formed in this way are insoluble in water and in the ordinary photographic developing and fixing baths although No. 2,306,410, granted December 29,

the silver images formed simultaneously with them may be removed from the photographic layer.

Many of the phenolic and naphtholic coupler compounds hitherto used are not sufficiently soluble in the developing solution to enable them to be incorporated in sumciently large amounts and some of them also tend to produce cloudy or hazy dye images. For these reasons the images as high dye density as desired and the resulting picture is not clearly transparent.

It is, therefore, an object of the present invention to provide novel photographic coupler compounds having desirable characteristics. A further object is to provid photographic couplers which are highly soluble in developing solutions. A still further object is to provide photographic couplers which produce transparent dyes on photographic development. A still .further object is to provide coupler compounds which form dyes of desirable transmission characteristics for multi-color photography.

These objects are accomplished by using as couplers phenolic or naphtholic compoiindscon-- taining at least one sulphonamide group.

The compounds preferably used as couplers according to my invention are a-naphthols .containing. a sulphonamide group (-SOaNI-Iz). The naphthols may contain substituent groups in the rings and the amino group ofthe sulphonamide substituent may also be substituted at one or both of the hydrogen atoms. Two or more sulphonamide groups may be present in the comhnl'l'hfl nllzhnuo'h than nail-inn nit-kn an new: mil-h respect to the hydroxyl group of the naphthol should preferably be free, or substituted with a replaceable group, since it appears likely that the coupling occurs in one of these positions.

Examples of coupler compounds suitable for use according to my invention are as follows:

a-Naphthol-4-chloro-8-sulphonam I OH NHIS (m-s OzNHi a-Naphthol-3:6-dis\flphonamide SOr-NHCQHI l-naphthol-5-sulphonanillde s ORNHOGHI 2,4-dichloro-l-naphthol-5-sulphonauilido HO I GHQ-CHI CH:C Hz l-naphthol-B-sulphopiperidide o v H cm-cn s 05-NH-0 on.

our-om N-cyclohexyl-l-naphthol-b-sulphonamide CHI-CH:

no s o i 011,

carom a-Naphthol-8-sulphonamide l-naphthol-o-benzoylaminotsulphonanilide OH NH-C -031 CtHtNHSO SOaNECnHl l-napthol-8-acetamlno-3,c-disulphcnanilide In place of the e-naphthols containing a sulphonamide described above, I may also use p-naphthols or phenols. These compounds may contain substltuent groups -in the ring or rings of the phenolic or naphthoic portion of the molecule as illustrated above or one or both hydrogen atoms of the NH: group of the sulphonamide may be substituted as indicated in the above examples. The following example, which is illustrative only, indicates a developing solution which may be used according to my invention.

Dimethyl-p-phenylenediamine sulphate grams" 2.5 Sodium sulphite -anhydrous. do 2 Sodium carbonate anhydrous do 20 Potassium bromide do 1 Water to '1000 I-naphthoI-S-sulphonanilide -grams 2 Igopropyl alonhnl on 100 For use, 3 is added to A.

In the foregoing examples, I'have described adding the coupler compound to the developing solution itself. However, the coupler compound may be' incorporated inv the photographic layer prior to exposure and the colored image formed by development in the primary aromatic amino developing solution. Special dispersing agents may be used for incorporating the coupler compound in the emulsion and in certain cases the coupler compound may be absorbed or adsorbed to the sensitive salt or may be combined with the sensitive silver salt as a chemical combination. In the case of a multi-layer photographic film in which the color-forming compounds may be incorporated in one or more layers of thefilm, it may be necessary to take special precautions to prevent wandering oi the coupler compound from the sensitive layer in which it is incorporated.

The aromatic amino developing agents used with the coupler compounds of our invention include the mono, di and tri-aminoa'ryl compounds and their derivatives formed by substitution in the amino group as well as in the ring, such as alkylphenylenediainines and alkyltoluylenediamines. These compounds are usually used in the salt form, such as the hydrochloride or the sulphate, which are more stable than the amines themselves. Suitable compounds are diethyl-pphenylenediamine hydrochloride, monomethylp-phenylenediaminehydrochloride, and dimethyl-,

p-phenylenediaminesulphate. The p-aminophenols and their substitution products may also be used where the amino group is unsubstituted. All of these compounds have an unsubstituted amino group which enables the oxidation products cf the developer to couple with the color forming compounds to form a dye image.

My development process may be employed for the products of colored photographic images in layers of gelatin or other carrier, such as collodion, organic esters of cellulose or synthetic resins. The carrier may be supported by a transparent medium such as glass as a cellulose ester or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support or in the caseoi a transparent support as superposed layers on one or both sides of the support. The superposed layers may be differentially sensitized and the dyes formed therein by coupling may be bleached by an oxidizing agent such as chromic acid +KBr to colorless soluble compounds. The destruction of the dye in this waydoes not destroy the silver image and a silver image may be developed, bleached and developed to color a number of times, thus permitting the formation of natural color images and superposed layers as described, for example, in Mannes and Godowsky U. S. Patent No. 2,113,329.-

- The examples and compounds set forth in the present specification are illustrative only and it is to be understood that my invention is to be taken as limited only by the scope of the appended claims.

Iclaim:

1. A color-forming photographic developer comprising an aromatic amino developing agent and a coupler compound selected from the group consisting of phenols and naphthols containing at least one sulphonamide group.

2. A color-forming photographic developer comprising an aromatic amino developingagent naphthol containing at least one sulphonamide 5. A color-forming photographic developer comprising an aromatic amino developing agent and a coupler compound comprising a-naphthol- 8-su1phonamide.

6. IA color-forming photographic developer comprising an aromatic amino developing agent and acoupler compound comprising a-naphthol- 3:6-disulphonamide '7. The method of producing a colored photographic image in a gelatino-silver halide emulsion layer,- which comprises exposing it and developing it with an aromatic amino developing agent containing a primary amino group in the presence of a coupler compound selected from the group consisting of phenols and naphthols containing at least one sulphonamide group.

8. The method of producing a colored photographic image in a gelatino-silver halide emulsion layer, which comprises exposing it and developing it with an aromatic amino developing agent containing a primary amino group in the presence of an -naphthol containing at least one sulphonamide group. 7 i

9. A photographic emulsion for forming colored images comprising a carrier containing a l sulphonamide grou sensitive silver halide and a coupler compound selected from the group consisting of phenols and naphthols containing at least one sulphonamide 10. A photographic emulsion for forming colored images comprising a carrier containing a sensitive silver halide and comprising an u-naphthol containing at least one a coupler compound prising a gelatino-silver halide emulsion containv ing a coupler compound selected from the group 11. A color-forming photographic layer com-' KARL SCHINZEL. 

